WO2020178261A1

WO2020178261A1 - Layer structure for producing a hinge, in particular for producing multi-layered book covers

Info

Publication number: WO2020178261A1
Application number: PCT/EP2020/055488
Authority: WO
Inventors: Georgios Tziovaras; Heinz Pudleiner; Deivaraj Theivanayagam Chairman; Helge Kosthorst; Christoph KÖHLER; Norbert HERMANNS; Kira PLANKEN; Stefan Janke
Original assignee: Covestro Intellectual Property Gmbh & Co. Kg
Priority date: 2019-03-07
Filing date: 2020-03-03
Publication date: 2020-09-10
Also published as: EP3934907A1; CN113490590A; CA3125418A1; US20220184988A1; KR20210142100A; BR112021017570A2

Abstract

The present invention relates to a layer structure, preferably a hinge, particularly preferably a book cover, most particularly preferably a book cover for identification and security documents, comprising at least one outer layer a) containing at least one thermoplastic elastomer, preferably a thermoplastic polyurethane and at least one layer b) containing at least one material selected from the group consisting of a polymer, a metal, a textile, a paper and a synthetic paper or a combination of at least two thereof. The invention further relates to a laminate comprising the aforementioned layer structure and to the production method therefor. The invention further relates to the use of the layer structure and/or laminate in order to produce a hinge, preferably a multilayer book cover, in particular for security and identification documents.

Description

Layer structure for the production of a hinge, especially for the production of multi-layer book covers

The present invention relates to a layer structure, preferably a hinge, particularly preferably a book cover, very particularly preferably a book cover for identification and security documents, comprising at least one outer layer a) containing at least one thermoplastic elastomer, preferably a thermoplastic polyurethane and at least one layer b) Containing at least one material selected from the group consisting of a polymer, a metal, a textile, a paper and a synthetic paper or a combination of at least two thereof, as well as a laminate comprising the above layer structure and also its manufacturing process. The invention further relates to the use of the layer structure and / or laminate for producing a hinge, preferably a multi-layer book cover, in particular for security and identification documents.

Layer structures made of plastic layers enable a large number of applications in different areas, especially in the area of security and identification documents, layer structures have become indispensable. Especially for the provision of

For hinges, especially for the production of multi-layer book covers, it is important that the hinge is particularly durable even after being opened and closed several times. Furthermore, it is desirable to embed various functionalities in this layer structure. Particularly in the field of security and identification documents, a high demand for such documents is to be expected that reliably perform their function with regard to embedded

Meet security features and electronics and at the same time also offer protection against damage, counterfeiting and wear and tear. An example of such a security and

The identification document is the passport, for which it is difficult to check, especially with severe signs of wear, whether this passport was subject to an attempted forgery or not.

The passport book cover plays a special role in the security and longevity of a passport. The electronic part of a passport is usually incorporated into the passport book cover. Furthermore, the data page in the passport, which in many passports is made of paper and contains important security features of the passport (e.g. photo of the passport holder or a hologram), is protected.

Passport manufacturers are offered a variety of materials that can be used to make book covers. These materials are usually multi-layer composites made of plastic films, textiles, paper and other materials that are obtained in the form of sheets or in the form of rolls. These materials give the manufactured with it Book cover their color, grain and feel. The underlying layers of material serve to reinforce the book cover in order to accommodate electronic security elements such as a chip module or an antenna, if necessary, and to increase the tear resistance of the passport book cover, e.g. B. by incorporating fabric or plastic films.

When selecting the outer layer of a passport book cover, color, printability, feel, grain and resistance to wear and tear must be taken into account. Often the desired properties of the book cover cannot be adequately achieved with one material or with several material layers. So z. B. a sufficient resistance to wear and tear can only be achieved with difficulty with a textile layer, a high-quality leather feel cannot be achieved with a relatively hard and little grained outer layer.

Accordingly, the passport manufacturers have to process different materials in order to be able to meet the criteria of their clients. This increases the complexity in the production and thus the production costs. The complexity is further increased if a chip module and / or an antenna for contactless data transmission is to be integrated in the passport book cover. For this purpose, a further layer, usually a plastic film, is required which, depending on the position of the chip module, must have an opening in which the chip can be received. Due to this complexity, passport book covers are manufactured in parallel production steps. The part of the passport book cover with chip and antenna, known as the "inlay", is usually manufactured separately. Later, the prefabricated inlay and the remaining layers of the passport book cover are connected by lamination under pressure and heat.

DE-A 102006011388 discloses the production of a multi-layer passport book cover by lamination. Additional layers of adhesive are used to hold the laminate together. The fiber layer 18 requires a punching out in the area of the chip module. The cover layers 23, 24, 26 have the specified color, grain and feel.

EP-A 1790496 discloses the production of a passport book cover in which a layer of polyurethane is placed between two outer layers and is laminated under pressure and temperature. The polyurethane layer acts as an adhesive layer for the outer layers. The color, the grain, the feel are given by the outer layers. Separate manufacturing steps must be carried out for embedding the electronics.

WO-A 2010132117 discloses the production of a passport book cover in which the unevenness caused by the chip module is compensated for by a polyurethane foam. The polyurethane foam also serves as an adhesive between two layers. This is a particularly complex process because the foam is created by mixing two liquid Components are created that are applied to the surfaces to be bonded through a nozzle. The cover layer 19 has a predetermined color, grain, feel.

The multi-layer structures described so far include quite complex manufacturing processes and the desired requirements cannot always be implemented simply and without loss of properties.

It was therefore an object of the present invention to provide a layer structure, in particular for hinges, preferably for book covers, very particularly preferably for book covers of identification or security documents, which enables a variety of different requirement profiles using a few base materials and is also easy to process . In the case of book covers for identification or security documents in particular, it should be possible, in addition to color, grain, and haptics, to simply embed electronic security elements such as chip modules or antennas in the book cover by lamination. In addition, the layer structure, in particular for hinges, should preferably be used for book covers, very particularly preferably for book covers of identification or security documents, with regard to mechanical parameters such as e.g. Tear resistance, composite adhesion of the individual layers, abrasion resistance, represent an improvement on the passport book covers known from the prior art.

Another object of the invention is to provide a layer structure, in particular for hinges, preferably for book covers, very particularly preferably for book covers of identification or security documents, which has a long service life.

It is also an object of the invention to provide a layer structure, in particular for hinges, preferably for book covers, very particularly preferably for book covers of identification or security documents, which is composed at least in part of transparent or translucent materials. In particular, it was an object to adequately protect printed layers of the layer structure but still make them visible from the outside.

Surprisingly, this object could be achieved with a layer structure, preferably a hinge, particularly preferably a book cover, very particularly preferably a book cover for identification or security documents, comprising at least one outer layer a) containing at least one thermoplastic elastomer, in particular a thermoplastic polyurethane, preferably one thermoplastic polyurethane with a hardness of> 60 Shore A according to DIN ISO 7619-1 to <95 Shore D according to DIN ISO 7619-1, particularly preferably with a hardness of> 70 Shore A according to DIN ISO 7619-1 to <95 Shore A according to DIN ISO 7619-1, and at least one layer b) containing at least one material selected from the group consisting of a thermoplastic polymer, a metal, a textile, a paper and a synthetic paper or a combination of at least two thereof, particularly preferably at least one textile, a paper and / or a synthetic paper.

Layer a) can consist of a single film or a composite of at least two films. At least one of the films preferably has at least the thermoplastic elastomer, very particularly preferably at least two or all films. The film in layer a) which contains the thermoplastic elastomer is preferably the outermost film in the layer structure.

Thermoplastic elastomers are materials that contain elastomeric phases in thermoplastically processable polymers either physically mixed in or chemically bound. A distinction is made between polyblends in which the elastomeric phases are physically mixed and block copolymers in which the elastomeric phases are part of the polymeric structure. The structure of the thermoplastic elastomers means that hard and soft areas are next to each other. The hard areas form a crystalline network structure or a continuous phase, the spaces between which are filled by elastomeric segments. Due to this structure, these materials have rubber-like properties.

The thermoplastic elastomer is preferably selected from the group consisting of a thermoplastic copolyamide (TPE-A), in particular a polyether block amide, a thermoplastic polyurethane (TPE-U), a thermoplastic polyester elastomer (TPE-E), a styrene block copolymer (TPE-S), TPE-V - Vulcanized (cross-linked) PP / EPDM compounds or a mixture of at least two of these.

The thermoplastic copolyamide (TPE-A) can be any copolyamide that a person skilled in the art would select for a layer structure, in particular polyether block amides (PEBA). Preferred polyether block amides are, for example, those which consist of polymer chains which are built up from recurring units corresponding to formula 0.

in which

A is the polyamide chain derived from a polyamide with 2 carboxyl end groups by loss of the latter and

B is the polyoxyalkylene glycol chain derived from a polyoxyalkylene glycol with terminal OH groups by loss of the latter, and n is the number of units forming the polymer chain. The end groups are preferably OH groups or residues of compounds which terminate the polymerization.

The dicarboxylic acid polyamides with the terminal carboxyl groups are obtained in a known manner, e.g. by polycondensation of one or more lactams and / or one or more amino acids, furthermore by polycondensation of a dicarboxylic acid with a diamine, in each case in the presence of an excess of an organic dicarboxylic acid, preferably with terminal carboxyl groups. These carboxylic acids become part of the polyamide chain during the polycondensation and are deposited in particular at the end of the same, whereby an m-dicarboxylic acid polyamide is obtained. The dicarboxylic acid also acts as a chain terminator, which is why it is used in excess.

The polyamide can be obtained starting from lactams and / or amino acids with a hydrocarbon chain consisting of 4-14 carbon atoms, e.g. of caprolactam, oenantholactam, dodecalactam, undekanolactam, decanolactam, 11-amino-undecanoic or 12-aminododecanoic acid.

Examples of polyamides such as those formed by the polycondensation of a dicarboxylic acid with a diamine include the condensation products of hexamethylenediamine with adipic, azelaic, sebacic and 1,12-dodecanedioic acid, and the condensation products of nonamethylenediamine and adipic acid.

In the case of the dicarboxylic acids used for the synthesis of the polyamide, on the one hand to fix a carboxyl group at each end of the polyamide chain and on the other hand as a chain terminator, those with 4-20 carbon atoms come into consideration, in particular alkanedioic acids such as succinic, adipic, cork -, azelaic, sebacic, undecanedi- or dodecanedioic acid, and also cycloaliphatic or aromatic dicarboxylic acid, such as terephthalic or isophthalic or cyclohexane-1,4-dicarboxylic acid.

The polyoxyalkylene glycols having terminal OH groups are unbranched or branched and have an alkylene radical with at least 2 carbon atoms. In particular, these are polyoxyethylene, polyoxypropylene and polyoxytetramethylene glycol, and copolymers thereof.

The average molecular weight of these OH group-terminated polyoxyalkylene glycols can vary in a wide range; it is advantageously between 100 and 6000, in particular between 200 and 3000. The proportion by weight of the polyoxyalkylene glycol, based on the total weight of the polyoxyalkylene glycol and dicarboxylic acid polyamide used to produce the PEBA polymer, is preferably 5-85% by weight, preferably 10-50% by weight.

Processes for the synthesis of such PEBA polymers are from FR-PS 7 418 913, DE-OS 28 02 989, DE-OS 28 37 687, DE-OS 25 23 991, EP-A 095 893, DE-OS 27 12 987 respectively DE OS 27 16 004 known.

Those PEBA polymers which, in contrast to those described above, have a statistical structure are particularly suitable. To produce these polymers, a mixture of

1. one or more polyamide-forming compounds from the group of aminocarboxylic acids or lactams with at least 10 carbon atoms,

2. an a, w -dihydroxy-polyoxyalkylene glycol,

3. at least one organic dicarboxylic acid in a weight ratio of 1: (2 + 3) between 30:70 and 98: 2, with hydroxyl and carbonyl groups being present in equivalent amounts in (2 + 3), in the presence of 2 to 30 wt. -% water, based on the polyamide-forming compounds of group 1, heated under the autogenous pressure to temperatures between 23 ° C and 30 ° C and then after removing the water with the exclusion of oxygen at normal pressure or under reduced pressure at 250 to 280 ° C to be treated further.

Such preferred suitable PEBA polymers are e.g. in DE-OS 27 12 987 described.

Suitable and preferred suitable PEBA polymers are, for example under the trade names PEBAX, from the company Atochem., Pebax ^® 5010, Pebax ^® 5020, Pebax ^® 5030, Pebax ^® 5040, Pebax ^® 5070 Arkema (Germany), Vestamid Fa. Hüls AG, Grilamid from EMS-Chemie and Kellaflex from DSM.

The active ingredient-containing polyether block amides according to the invention can also contain the additives customary for plastics. Typical additives are, for example, pigments, stabilizers, flow agents, lubricants and mold release agents.

Thermoplastic copolyamides products such as Pebax ^® 5010, Pebax ^® 5020, Pebax ^® 5030, Pebax ^® 5040, Pebax ^® may be mentioned 5070 Arkema (Germany) as an example. Examples of thermoplastic polyurethanes will be mentioned later. The thermoplastic polyester elastomer (TPE-E) can be any polyester elastomer that a person skilled in the art would select for a layer structure; the polyester elastomers are preferably copolyesters. Suitable copolyesters (segmented polyester elastomers) are built up, for example, from a large number of recurring, short-chain ester units and long-chain ester units which are united by ester bonds, the short-chain ester units making up about 15-65% by weight of the copolyester and having the formula (I):

in which

R stands for a divalent radical of a dicarboxylic acid which has a molecular weight of less than about 350,

D is a divalent radical of an organic diol that has a molecular weight below about 250;

the long-chain ester units make up about 35-85% by weight of the copolyester and have the formula (II)

in which

G is a divalent radical of a long chain glycol that has an average molecular weight of about 350 to 6,000. Examples of thermoplastic polyester elastomer (TPE-E), DuPont ™ Hytrel ^® 5556 or DuPont ™ Hytrel ^® PC966 NC010 (Fa. DuPont, Wilmington, DE 19880-0709).

The copolyesters which can preferably be used can be prepared by polymerizing a) one or more dicarboxylic acids, b) one or more linear, long-chain glycols and c) one or more low molecular weight diols with one another.

The dicarboxylic acids for the production of the copolyester are the aromatic acids with 8-16 C atoms, in particular phenylenedicarboxylic acids such as phthalic, terephthalic and isophthalic acid.

The low molecular weight diols for the conversion to form the short-chain ester units of the copolyesters belong to the classes of acyclic, alicyclic and aromatic Dihydroxy compounds. The preferred diols have 2-15 carbon atoms, such as ethylene, propylene, tetramethylene, isobutylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene and decamethylene glycols, dihydroxycyclohexane, cyclohexanedimethanol, resorcinol, hydroquinone and the like . The bisphenols for the present purpose include bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) methane, bis (p-hydroxyphenyl) ethane and bis (p-hydroxyphenyl) propane.

The long-chain glycols for making the soft segments of the copolyester preferably have molecular weights of about 600 to 3000. They include poly (alkylene ether) glycols in which the alkylene groups have 2-9 carbon atoms.

Glycol esters of poly (alkylene oxide) dicarboxylic acids or polyester glycols can also be used as long-chain glycol.

The long-chain glycols also include polyformals, which are obtained by reacting formaldehyde with glycols. Polythioether glycols are also suitable. Poly-butadiene and polyisoprene glycols, copolymers of the same, and saturated hydrogenation products of these materials make satisfactory long-chain polymeric glycols.

Processes for the synthesis of such copolyesters are known from DE-OS 2 239 271, DE-OS 2 213 128, DE OS 2 449 343 and US-A 3 023 192.

The copolyesters can also contain the additives customary for plastics. Usual additives are for example lubricants such as fatty acid esters, their metal soaps, fatty acid amides and silicone compounds, antiblocking agents, inhibitors, stabilizers against hydrolysis, light, heat and discoloration, flame retardants, dyes, pigments, inorganic or organic fillers and reinforcing agents. Reinforcing agents are in particular fiber-like reinforcing materials such as inorganic fibers, which are produced according to the prior art and can also be treated with a size. More detailed information on the auxiliaries and additives mentioned can be found in the specialist literature, for example J.H. Saunders, K.C. Frisch: "High Polymers", Volume XVI, Polyurethane, Part 1 and 2, Interscience Publishers 1962 and 1964, R.Gächter, H. Müller (Ed.): Taschenbuch der Kunststoff-Additive, 3rd edition, Hanser Verlag, Munich 1989, or DE-A 29 01 774.

The thermoplastic styrene block copolymer (TPE-S) can be any styrene block copolymer that a person skilled in the art would select for a layer structure. The styrene-butylene block copolymers which can preferably be used consist of a polyethylene-butylene-rubber middle block with a polystyrene end block chemically coupled at both ends. The polystyrene content is less than 30%. The polystyrene end blocks are evenly distributed as spherical polystyrene domains in the ethylene rubber matrix.

Processes for the synthesis of suitable styrene block copolymers are known, for example, from US Pat. Nos. 3,485,787, 4,006,116 and 4,039,629. The styrene block copolymers can also contain the additives customary for plastics. Typical additives are, for example, pigments, stabilizers, flow agents, lubricants and mold release agents.

Examples of styrene block copolymers (TPE-S) are Elastron G, such as Elaston Gl 00 and G101, Elastron D, such as Elaston D100 and D101 from Elastron (Turkey) and Kraton ™ D SIBS from Kraton Polymers (USA), Septon ™, especially Septon ™ Q1250 or Septon ™ V9461 by Kuraray (Japan), Styroflex® ^® 2G66 Ineos Styrolution Group GmbH (Germany), thermal load ^® K from Kraiburg TPE (Germany) and Saxomer ^® TPE-S of PCW GmbH (Germany). Further suitable styrene-butylene block copolymers are available, for example, under the trade names 'Kraton G and' Elexar from Shell Chemie GmbH.

The thermoplastic, vulcanized (crosslinked) PP / EPDM compound can be any PP / EPDM compound that the person skilled in the art would select for a layer structure. Examples of PP / EPDM compounds are Santoprene (from Exxon Mobil) or Sariink (from DSM).

The material of the at least one outer layer a) is preferably translucent or transparent; the material of the at least one outer layer a) is particularly preferably transparent.

The layer structure according to the invention is characterized in that the color, grain and feel of the outer layer can be implemented individually. In addition, the layer structures according to the invention have, after lamination, not only high bond strength but also very good mechanical stabilities with regard to tear resistance and abrasion resistance. The layer structures according to the invention also exhibit these properties over a period of several years. Furthermore, the layer structures according to the invention have a self-closing function after lamination and folding.

In addition, the layer structure can preferably emit odors, such as leather odor, through the addition of aromatic substances in layer a). Layer a) preferably has aromatic substances such as LEATHER WOODY from Drom or SUEDERAL IFF from Ventos in an amount in a range from 0.1 to 1% by weight, preferably in a range from 0.2 to 0.8% by weight, particularly preferably in a range from 0.3 to 0.7% by weight, based on the total weight of the layer a).

In one embodiment, the layer structure, preferably the hinge, particularly preferably the book cover, very particularly preferably the book cover for identification or security documents, has a length x and a width y, the at least one layer b) having at least one recess in any shape having. In another embodiment, the recess in layer b) of the layer structure, as described above, has the shape of a parallelogram which runs parallel to a line of symmetry of length x or width y, preferably the parallelogram has a width of> 0.1 mm to <100 mm, preferably from> 1.0 mm to <50 mm, particularly preferably from> 1.5 mm to <30 mm, very particularly preferably the parallelogram extends over the entire length x or over the entire width y.

In a further embodiment of the above layer structure, the at least one recess in layer b) has a width of> 0.1 mm to <100 mm, preferably> 1.0 mm to <50 mm, particularly preferably> 1.5 mm to <30 mm, and particularly preferably formed over the entire length of the layer structure, or the recess of layer b) is arranged in the form of at least two sections on layer a), so that between the at least two sections at least one recess on the layer a) is formed which is not covered by the layer b), and wherein the at least one recess preferably over a length of> 0.1 mm to <100 mm, preferably from> 1.0 mm to <50 mm, particularly preferred from> 1.5 mm to <30 mm, and particularly preferably over the entire width of the layer structure.

In a further embodiment of the layer structure described above, the layer b) can comprise one or more further cutouts in any shape.

The outer layer a) of the layer structure according to the invention contains at least one thermoplastic polymer, preferably a thermoplastic elastomer, as already described. The thermoplastic polymer preferably has a hardness of> 60 Shore A according to DIN ISO 7619-1 to <95 Shore D according to DIN ISO 7619-1, particularly preferably a hardness of> 70 Shore A according to DIN ISO 7619-1 to <95 Shore A according to DIN ISO 7619-1.

In a preferred embodiment of the layer structure, the outer layer a) contains at least one thermoplastic polyurethane (TPU), preferably a TPU with a hardness of> 60 Shore A according to DIN ISO 7619-1 to <95 Shore D according to DIN ISO 7619-1, in particular preferably with a hardness of> 70 Shore A according to DIN ISO 7619-1 to <95 Shore A according to DIN ISO 7619-1.

The outer layer a) preferably contains a thermoplastic polyurethane in an amount in a range from 50 to 100% by weight, more preferably in a range from 60 to 95% by weight, particularly preferably in a range from 70 to 85% by weight. -%, based on the total weight of the layer a).

Depending on the organic diisocyanates used, TPUs can have an aliphatic or aromatic character. TPU usually have a block or segment structure. A basic distinction is made between hard and soft segments. Hard segments are formed from the organic diisocyanates used for the reaction and short-chain ones

Compounds with two to three hydroxyl, amino, thiol or carboxyl groups, preferably compounds with two hydroxyl, amino, thiol or carboxyl groups, particularly preferably diols, with an average molecular weight of 60 to 500 g / mol. Soft segments are formed from the organic diisocyanates and long-chain ones used for the reaction

Compounds with two to three hydroxyl, amino, thiol or carboxyl groups, preferably compounds with two hydroxyl, amino, thiol or carboxyl groups, particularly preferably diols, with an average molecular weight of> 500 and <5000.

Hard segments contribute to the strength and the upper usage temperatures of the TPU's property profiles, while soft segments contribute to the elastic properties and low temperature flexibility to the material properties of the TPU.

Both for the hard segments and for the soft segments, aromatic, aliphatic, araliphatic, heterocyclic and cyclo aliphatic diisocyanates or mixtures of these diisocyanates can be used as organic diisocyanates (cf. HOUBEN-WEYL "Methods of Organic Chemistry", Volume E20 "Macromolecular Substances", Georg Thieme Verlag, Stuttgart, New York 1987, pp. 1587-1593 or Justus Liebig's Annalen der Chemie, 562, pages 75 to 136).

The following may be mentioned by way of example: aliphatic diisocyanates, such as hexamethylene diisocyanate, cycloaliphatic diisocyanates, such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and 2,2'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4 -Tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, mixtures of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4, 4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate, 4,4'-diisocyanatodiphenyl-ethane (1,2) and 1,5-naphthylene diisocyanate. 1,6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, diphenylmethane diisocyanate isomer mixtures with a 4,4'-diphenylmethane diisocyanate content of> 96% by weight and in particular 4,4'-diphenylmethane diisocyanate and 1 , 5-naphthylene diisocyanate. The diisocyanates mentioned can be used individually or in the form of mixtures with one another. They can also be used together with up to 15% by weight (calculated on the total amount of diisocyanate) of a polyisocyanate, for example triphenylmethane-4,4 ', 4 "-triisocyanate or polyphenyl-polymethylene-polyisocyanates. Particularly preferred organic diisocyanates are for example 4.4 Diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate and hexamethylene diisocyanate.

The preferred short-chain diols with a molecular weight of 60 to 500 g / mol are preferably aliphatic diols with 2 to 14 carbon atoms, for example ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol , 1,5-pentanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol. However, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms are also suitable, e.g. Terephthalic acid bis-ethylene glycol or terephthalic acid bis-1,4-butanediol, hydroxyalkylene ethers of hydroquinone, e.g. 1,4-di (ß-hydroxyethylj-hydroquinone, ethoxylated bisphenols, for example 1,4-di (ß-hydroxyethyl) bisphenol A, (cyclo) aliphatic diamines such as isophoronediamine, ethylenediamine, 1,2-propylenediamine, 1,3 - Propylenediamine, N-methyl-propylen-1,3-diamine, N, N'-dimethylethylenediamine and aromatic diamines such as 2,4-tolylenediamine, 2,6-tolylenediamine, 3,5-diethyl-2,4-tolylenediamine or 3,5-Diethyl-2,6-tolylenediamine or primary mono-, di-, tri- or tetraalkyl-substituted 4,4'-diaminodiphenylmethanes, ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4 are particularly preferred -Butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,4-di (β-hydroxyethyl) hydroquinone or 1,4-di (β-hydroxyethyl) bisphenol A can also be used. Mixtures of the above-mentioned compounds can also be used Smaller amounts of triplets can also be added.

The long-chain compounds with two to three hydroxyl, amino, thiol or carboxyl groups, preferably compounds with two hydroxyl, amino, thiol or carboxyl groups, particularly preferably diols, with a number average molecular weight of> 500 and <5000 can be divided into two Main groups are divided into: polyether diols and polyester diols. The polyether diols are based, for example, on polytetrahydrofuran, polyethylene oxide and polypropylene oxide and mixtures thereof. The polyester diols are typically based on adipates, e.g. 1,4-butanediol adipate and 1,6-hexanediol adipate and caprolactone. Cocondensates are also possible.

In the production of the TPU, catalysts known and customary according to the prior art can be used. These can be tertiary amines, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylamino-ethoxy) ethanol, diazabicyclo [2.2.2] octane and similar, and in particular organic metal compounds such as titanic acid esters , Iron compounds or tin compounds such as tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate or dibutyltin dilaurate or the like. Preferred catalysts are organic metal compounds, in particular titanic acid esters, iron and tin compounds. The total amount of catalysts in the TPU can generally be from about 0 to 5% by weight, preferably from 0 to 2% by weight, based on the total amount of TPU.

Furthermore, the TPU can contain auxiliaries and additives up to a maximum of 20% by weight, based on the total amount of TPU. Typical auxiliaries and additives are pigments, dyes, flame retardants, stabilizers against aging and weathering, plasticizers, lubricants and mold release agents, fungistatic and bacteriostatic substances and fillers and mixtures thereof.

Examples of further additives are lubricants, such as fatty acid esters, their metal soaps, fatty acid amides, fatty acid ester amides and silicone compounds, antiblocking agents, inhibitors, stabilizers against hydrolysis, light, heat and discoloration, flame retardants, dyes, pigments, inorganic and / or organic fillers, for example polycarbonates, as well as plasticizers and reinforcing agents. Reinforcing agents are, in particular, fibrous reinforcing materials such as e.g. inorganic fibers which are manufactured according to the state of the art and which can also be treated with a size. More detailed information on the auxiliaries and additives mentioned can be found in the specialist literature, for example the monograph by J.H. Saunders and K.C. Frisch "High Polymers", Volume XVI, Polyurethane, Part 1 and 2, Interscience Publishers 1962 and 1964, the pocket book for plastic additives by R.Gächter u. H. Müller (Hanser Verlag Munich 1990) or DE-A 29 01 774 can be found.

Suitable TPUs are available on the market, for example, under the trade names Desmopan ™, Elastollan ™, Pellethane ™, Estane ™, Morthane ™ or Texin ™.

The TPU of the at least one outer layer a) which can be used with preference or according to the invention can be used continuously in the so-called extruder process, e.g. in a multi-screw extruder, or in the so-called belt process. The dosage of the TPU described above, optionally with the auxiliaries and additives described above, can be carried out simultaneously, i.e. in the one-shot process, or in succession, i.e. by a prepolymer process. The prepolymer process is particularly preferred. The prepolymer can be introduced batchwise or continuously in part of the extruder or in a separate prepolymer unit connected upstream, e.g. a static mixer reactor, e.g. Sulzer mixers.

The at least one outer layer a) is preferably in the form of a single or multi-layer TPU film and can be produced by melting the preferred or inventive TPU granules in a melting extruder and using a nozzle to form a film with a thickness of> 20 pm to <1000 pm, preferably from> 50 pm to <800 pm, particularly preferably from> 100 pm to <450 pm. The at least one outer layer a) can be produced by the melt extrusion processes known to the person skilled in the art, the blow extrusion process and / or the cast extrusion process. For this purpose, the corresponding above-described TPU granules of the individual layers are melted in a melting extruder and extruded through a nozzle to form a film in corresponding layer thicknesses.

In one embodiment, the outer TPU layer can also comprise a dye and / or a pigment for coloring the outer layer. Alternatively, a full-area and / or partial-area printing layer can be applied to the at least one outer TPU layer. The outer TPU layer is preferably transparent.

The at least one layer b) according to the invention contains a material selected from the group consisting of a polymer, a metal, a textile, a paper and a synthetic paper or a combination of at least two of these, particularly preferably at least one textile, a paper and / or a synthetic paper.

The polymer can be a thermoplastic polymer selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds and / or polyaddition products of bifunctional reactive compounds, or mixtures thereof. Particularly suitable thermoplastic polymers are polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or copolymethacrylates such as, for example and preferably, polymethyl methacrylate (PMMA), poly or copolymers with styrene such as, for example and preferably, polystyrene (PS) acrylonitrile-butadiene-styrene (ABS) or polystyrene acrylonitrile (SAN), thermoplastic polyurethanes, and polyolefins, such as, for example and preferably, polypropylene types or polyolefins based on cyclic olefins (eg TOPAS ™), poly or copolycondensates of an aromatic dicarboxylic acid and aliphatic, cycloalophatic and / or araliphatic diols with 2 to 16 carbon atoms, such as, for example and preferably, poly- or copolycondensates of terephthalic acid, particularly preferably poly- or copolyethylene terephthalate (PET or CoPET), glycol-modified PET (PETG), glycol-modified poly- or copolycyclohexanedimethylene terephthalate (PCTG) or poly- or copolybutylene terephthalate (PBT or CoPBT), preferably polycondensates or copolycondensates of naphthalenedicarboxylic acid, particularly preferably polyethylene glycol naphthalate (PEN), poly- or copolycondensate (s) of at least one cycloalkyldicarboxylic acid, such as, for example and preferably, polycyclohexane-pcanedethanol), polycyclohexane-pcanedethanol), Polyvinyl halides, such as, for example and preferably, polyvinyl chloride (PVC), or their mixtures or blends of at least two of the aforementioned, particularly preferably one or more polycarbonates or copolycarbonates based on diphenols, poly- or Copoly (meth) acrylates, poly- or copolycondensates of terephthalic acid or their mixtures or blends of at least two of the aforementioned.

The polymer can also be at least one thermosetting plastic. This at least one thermosetting plastic can be selected from polymers of ethylenically unsaturated monomers and / or polycondensates of trifunctional reactive compounds and / or polyaddition products of trifunctional reactive compounds, or their mixtures of at least two of the aforementioned. These are, for example, hardenable molding compounds, Formadhehyd molding compounds, such as phenoplasts, phenol (PF), cresol (CF), resorcinol (RF), xylenol (XF) formaldehyde resins, aminoplasts such as urea - (UF) -, melamine (MF) -, furan (FF) formaldehyde resins and other materials such as prepregs, unsaturated polyester resins (UP), vinyl ester resins (VE), phenacrylate resins (PHA), epoxy resins (EP), diallyl phthalate resins and / or polydiallyl phthalate resins (PDAP), silicone resin (Si). Metals can be thin layers of steel, aluminum, copper, titanium or even more noble metals such as gold, silver, platinum and alloys of the above metals.

A textile can contain natural fibers (e.g. rock wool, cotton, flax, hemp, wool, silk, fur hair) or chemical fibers (cellulose, polyacrylonitrile, polypropylene, polyester, polyamide, polyurethane, ceramic, glass, metal) and, if necessary, additional non-textile raw materials (e.g. Leather, feathers, metals).

A paper essentially comprises fibers of vegetable origin, whereas synthetic paper comprises exclusively plastic fibers, preferably polyethylene or polypropylene fibers. Layer b) preferably contains paper and / or synthetic paper. In particular for the use of the layer structure according to the invention in the area of security and identification documents, synthetic paper such as Teslin ™ from PPG can be advantageous. The use of Teslin ™ can be particularly advantageous as a carrier for chip modules and / or antennas, especially in security and identification documents, since these chip modules and / or antennas can easily be attached to Teslin ™, e.g. using ultrasonic methods.

In a preferred embodiment, the at least one layer b) comprises at least one dye and / or at least one pigment; optionally, layer b) can additionally comprise a print layer that is applied over the entire and / or part of the area.

In another embodiment, the at least one layer b) comprises a printing layer which can be applied over the entire area and / or over part of the area and wherein the printing layer points in the direction of layer a). The layer b) can have a thickness in the range from 40 µmi to <800 µm, preferably from> 80 µm to <500 µm, particularly preferably from> 100 µm to <300 µm.

In a further embodiment, the layer structure comprises at least one further layer c) containing at least one thermoplastic polyurethane, which is at least partially configured as a foam layer, and at least one further layer b ′) containing at least one material selected from the group consisting of a polymer, a metal , a textile, a paper and a synthetic paper or a combination of at least two of these, particularly preferably at least one textile, a paper and / or a synthetic paper. At least one component and / or one functional unit is preferably positioned on the at least one further layer b ′). Preferably, the at least one component and / or the functional unit is at least partially surrounded by the at least one layer c) or completely encased by the at least one layer c), preferably completely encased by the at least one layer c).

The at least one further layer b ') preferably has a recess in any shape, preferably in the form of a parallelogram which runs along a line of symmetry to the length x or width y of the layer structure, particularly preferably the recess in layer b') is so arranged that this corresponds in shape and position to the recess in layer b).

With regard to the material, layer thicknesses and preferred embodiments of the at least one further layer b ′), reference is made to the above statements of layer b) in order to avoid unnecessary repetitions. Layer b ′) can be identical to or different from layer b) with regard to material and layer thickness. In a preferred embodiment, layers b) and b ') comprise the same materials and layer thicknesses on, preferably paper and / or synthetic paper.

Any number of components and / or functional units can be placed on layer b '). Possible components and / or functional units are, for example, sensors, chip modules, data storage media, batteries, lighting units and / or also components and / or functional units connected to one another. These components and / or functional units can have thicknesses in the range from 20 μm to 1500 μm.

The at least one component and / or functional unit is preferably placed on the layer b ′) in such a way that it is at least partially covered by the at least one layer c), that is to say the layers form the immediate sequence a) b) c) b ′).

The at least one further layer c) containing at least one TPU is designed as a foam layer at least in some areas. In principle, all thermoplastic polyurethanes are possible (TPU) to foam by adding suitable blowing agents. TPUs are preferably chosen which have a low hardness. This minimizes the risk of damaging the electronic components during lamination. The thermoplastic polyurethanes of layer c) preferably have a hardness of> 60 Shore A according to DIN ISO 7619-1 to <95 Shore D according to DIN ISO 7619-1, preferably> 70 Shore A according to DIN ISO 7619-1 to <95 Shore A according to DIN ISO 7619-1.

The at least one layer c) preferably has a density of> 0.2 to <0.9 g / cm ³ , preferably of> 0.3 to <0.8 g / cm ³ , particularly preferably of> 0, prior to lamination, 5 to <0.7 g / cm ³ . Before the lamination, the pores in the at least one layer c) preferably have a diameter between 50 μm and 250 μm.

To produce the preferred foam layer c), a blowing agent is added to the TPU, preferably a blowing agent which splits off CO 2 when heated and thus forms the foam layer. Suitable propellants are hydrogen carbonates such as calcium hydrogen carbonate, potassium hydrogen carbonate and / or sodium hydrogen carbonate, and / or citrates such as sodium citrate, potassium citrate, calcium citrate, magnesium citrate.

To produce the foam layer c), the granular TPU is usually mixed as a masterbatch which contains a blowing agent. This mixture is then compressed, melted and homogenized in an extruder. The temperatures of the melt in the extruder are above the decomposition temperature of the blowing agent and CO2 is split off, most of which dissolves in the melt under the existing pressure. The melt is passed through an extrusion tool, which is also known as a nozzle. As a result of the pressure drop when exiting the nozzle, the CO2 dissolved in the melt is released and produces finely distributed bubbles. This foamed melt plume can be processed into a foamed film by means of further processing in the flat film or blown film process.

In both processes, further layers comprising at least one thermoplastic polymer, preferably TPU, can be coextruded with or without a blowing agent.

In a further embodiment, the layer structure comprises at least one further layer d) containing at least one thermoplastic polyurethane with a hardness of> 60 Shore A according to DIN ISO 7619-1 to <95 Shore D according to DIN ISO 7619-1, the layers being arranged in this way that the sequence a) b) d) c) b ') or a) b) c) d) b') results. In this embodiment, the at least one component and / or functional unit on layer b ′) is at least partially covered by layer c) or d). In another embodiment, the layer structure comprises at least one further layer d ′) comprising at least one thermoplastic polyurethane with a hardness of> 60 Shore A according to DIN ISO 7619-1 to <95 Shore D according to DIN ISO 7619-1, the layers being arranged in this way are that the sequence a) b) d) c) d ') b') or a) b) d ') c) d) b') results. In this embodiment, the at least one component and / or functional unit on layer b ′) is at least partially covered by layer d ′) or d).

As already described above for layer a), layers d) and d ') can be produced by the melt extrusion processes known to the person skilled in the art, the blow extrusion process and / or the cast extrusion process. For this purpose, the corresponding above-described TPU granules of the individual layers can be melted in a melting extruder and extruded through a nozzle to form a film in appropriate layer thicknesses.

To avoid repetition, reference is made to the above with regard to materials, composition, production and embodiments of the TPU of layers c), d) and d ').

The at least one TPU of layers c), d) and d ') can be identical or different independently of one another; the at least one TPU is preferably the same.

The layer thickness of layers d) and / or d ') can independently of one another have thicknesses from> 5 μm to 150 μm, preferably from 10 μm to 120 μm, particularly preferably from 15 μm to 110 μm, these are preferred equal.

In another embodiment of the invention, the at least one layer d) and / or d ') can be used in the form of a single-layer or multilayer film.

In one embodiment of the invention, the at least one further layer c) and the at least one further layer d) are contained in the layer structure in the form of a multilayer film c) d), preferably in the form of a multilayer co-extruded film c) d).

In another embodiment, the at least one layer c), the at least one further layer d) and the at least one further layer d ') are in the form of a multilayer film d) c) d') in the layer structure, the at least further layers d ) and d ') enclose the at least one layer c). It is preferably a multilayer, co-extruded film with at least the layer sequence d) c) d '), particularly preferably in the form of a three-layer co-extruded film with the layer sequence d) c) d ″). The layers c), if appropriate d) and if appropriate d ') can have a total layer thickness of 100 to 1200 µm, preferably 300 to 800 µm, particularly preferably 350 to um 550 µm, before lamination. In particular, the thickness of the layer c) can be selected such that this layer c) completely envelops the component and / or the functional unit.

In particular when using the layer structure according to the invention for the production of hinges, preferably book covers, especially for the production of book covers of security and identification documents, further layers can be built up facing inwards, i.e. the inside of the hinge, preferably the book cover. For example, a further layer a ') can be placed on layer b'), followed by a further layer b "), preferably paper and / or synthetic paper, which is preferably printed, so that the following exemplary layer structures can be implemented Layer a ') acts as an adhesive layer to connect layer b "), preferably paper, to the rest of the structure:

a) b) d) c) b ') a) b ")

a) b) c) d) b ') a) b ")

a) b) d) c) d ') b') a) b ")

a) b) d ') c) d) b ") a) b")

The invention also relates to a method for producing a multilayer laminate comprising at least the steps

i) providing a layer structure according to the invention as described above with the corresponding embodiments and preferred areas;

ii) Lamination of the layer structure from step i) at a temperature of> 80 ° C to <220 ° C and a pressure of> 2 N / cm ² to <500 N / cm ² , preferably lamination with an engraved lamination sheet, particularly preferably with an engraved lamination sheet comprising an anti-stick coating.

For the production of hinges, in particular for the production of book covers, especially for the production of book covers for security and identification documents, the method can also include the following steps after step ii):

iii) extending the layer structure, preferably along the recess in layer b) and optionally in layer b ');

iv) pressing of the layer structure according to step iii) along the recess in layer b) and optionally in layer b '), preferably pressing between two rollers, rollers and / or plates, at a temperature which is> 0.5 ° C to <150 ° C, preferably> 1 ° C to <50 ° C, particularly preferably> 1 ° C to <20 ° C, above the softening temperature of the outer TPU layer a) for a period of 2 to 20 seconds, preferably 2 to 10 seconds, particularly preferably 2 to 5 seconds;

v) Removal of the layer structure from the press.

In step iv), pressure is exerted on the laminated layer structure in the region of the fold by means of temperature-controlled rollers, rollers and / or plates in order to permanently deform the laminated layer structure. This creates the desired flat position of the laminated layer structure when it is closed. In particular for the use of the layer structure according to the invention for the production of security and identification documents, the maximum open position of a closed layer structure according to ISO IEC 18745-1 should not exceed a height of 10 mm. In particular when pressure is exerted on the layer structure in the region of the fold for a period of 2 to 20 seconds, in particular from 2 to 5 seconds and at a temperature which is> 0.5 ° C to <150 ° C, preferably> 1 ° C to <50 ° C, particularly preferably> 1 ° C to <20 ° C, above the softening temperature of the outer TPU layer a), a self-closing function of the folded layer structure can be implemented, which is particularly useful in the production of security and identification documents for example, can be advantageous as a passport book cover.

In a preferred embodiment of the method, in particular a method for producing a book cover, particularly preferably a method for producing a book cover for security and identification documents, the method further comprises the steps

vi) inserting one or more additional insert sheets into the book cover;

vii) Insertion of a seam through the book cover and the insert sheets or fixation of the insert sheets by means of adhesive strips.

The lamination with engraved laminating sheets can enable the introduction of the desired haptics on the outside of the layer structure according to the invention. Laminating sheets with non-stick coating are preferably used in order to prevent a bond between the outer TPU layer and the laminating sheet.

Usual anti-stick coatings for metals can be Teflon layers or very thin crystal layers, which are applied to metals under vacuum. For example, Teflon coatings from Adelhelm, or crystal coatings from Plascotec (Placosam ™ coating). The desired graining of the outer layer is created using the corresponding graining of the laminate sheet. During the lamination process, the grain is transferred from the sheet metal to the TPU layer. The transfer is particularly accurate, even with fine engravings, so that finely matted sheets produce finely matted TPU outer layers and shiny sheets lead to shiny TPU outer layers. The graining of the surface also changes the feel of the passport book cover in addition to its visual appearance Keeping the same TPU layer. Shiny surfaces feel sticky, matt surfaces or surfaces with a leather grain feel almost like leather surfaces.

The invention further provides a laminate comprising the layer structure according to the invention described above.

The invention also relates to the use of the above-described layer structure according to the invention for producing a hinge, preferably for producing a multi-layer book cover, in particular a book cover for security and identification documents. It is also possible to use the laminate according to the invention to produce a hinge, for example for bags, purses, pencil cases, card holders.

Examples

Raw materials and materials of the individual layers

Layer a)

An aliphatic polycaprolactone-based TPU with a Shore A hardness of 85-90 according to ASTM D2240 or DIN ISO 7619-1 was used to produce the outer TPU layer of a passport book cover (Figure 1, layer a). The melt extrusion process was used to manufacture the TPU film. The TPU granules were melted in the melting extruder and extruded through a nozzle to form a film with a thickness of 150 μm. Layer b) and b ')

For layer b) and IT) a 250 μm thick synthetic paper from PPG was used, which is sold under the trade name Teslin ™.

Film 1: 3 -layer film with the layer sequence dcd ') A three-layer thermoplastic polyurethane film with a thickness of 600 μm was produced in the blow-coextrusion process. The film consisted of three layers: the two outer layers d) each made of 100 μm compact thermoplastic polyurethane and the 400 μm thick middle layer c) made of foamed thermoplastic polyurethane. The thermoplastic polyurethane used was a TPU based on polytetrahydrofuran (molecular weight 2000), 4,4'-methylenediphenylene diisocyanate and 1,4-butanediol as a chain extender with a Shore A hardness of 87, measured according to DIN ISO 7619-1, corresponding to a hardness of 36 Shore-D measured according to DIN ISO 7619-1, a density of 1.12 g / cm3 measured according to DIN EN ISO 1183-1A and a melt flow index (MFI) of 30 g / 10 min measured at 190 ° C / 21.6 kg (DIN ISO 1133) is used. For foaming the middle layer c), the TPU used 5% by weight Hydrocerol ™ CF20 from Clariant, which releases CO2 when the film is heated in the extruder and thus foamed the TPU as it exited the nozzle.

Foil 2: 2-layer foil with the layer sequence (g-h) as an alternative layer a)

Shift (g-h)

For the production of the outer layer a) in the form of a layer sequence (gh) of a passport book cover, as shown in Figure 6, a polyether block amide (PEBA) was used for layer (g), together with a TPU for layer (h). The melt coextrusion process was used to produce layer a) in the form of the two-layer film (gh). The PEBA granulate and the TPU granulate were in separate melt extruders at 190 ° C to 200 ° C, preferably at 200 ° C., melted and extruded through a coextrusion nozzle to form a film with a thickness of 150 mhi.

Example 1: Passport book cover with TPU outer layer with coloring and lettering

Layer b) was printed in full color on one side. Printing was carried out by means of toner printing on a printer from the manufacturer Ricoh, model MP C3003. In addition to the full-surface color printing, the “Passport” lettering was printed on the already colored layer b).

The layer a) was arranged in such a way that it was in contact with the printed side of the layer b) so that the print was visible through the transparent layer a).

A line was marked on layer b) where the passport book cover should later be folded. The material of layer b) was removed along these fold lines to a width of 6 mm. For this, layer b) was placed in a press from Plator and a 6 mm wide strip of material was punched out along the fold line by means of a steel strip.

Layers a) and b) were stacked as shown in Figure 1) and fixed in their position by spot welding at the four corners of the curve.

The stack of layers a) and b) was laminated on a Bürkle lamination press. A fully engraved fiber sheet with a non-stick coating was used as the laminating sheet that was in contact with layer a). The engraving corresponded to a feather grain. The corresponding sheet was supplied by 4-Plate.

Famination parameters:

Preheat the press to 150 ° C.

Press for 5 minutes at a pressure of 20 N / cm ² .

Cool down under a pressure of 150 N / cm ² until a temperature of 38 ° C. has been reached and open the press.

After removing the laminate, the side that was in contact with the engraved sheet had a uniform feather grain, which could also be perceived as a feather. The adhesion of all layers was particularly good, so that a non-destructive separation and reuse of the layers was not possible. The separation of the layers was checked by trying to separate the individual layers from one another by hand. The layers could only be separated using appropriate tools (scissors, pliers), which resulted in damage to the layers. The color print remained undamaged after the contamination and appeared with good brilliance through the transparent outer layer a). A passport book cover of the desired size was punched out of the laminate. The punched-out book cover was then folded along the punched-out recess in the fold line. The folded side of the book cover was then clamped in a roll laminator to a width of 4 mm along the entire length of the book cover. The book cover was clamped for a period of 3 seconds at a roller temperature of 130 ° C. The book cover was then removed from the rollers. This enabled a memory effect to be achieved in position a): If the original shape of the book cover was disturbed by opening the book cover, it closed again automatically (Figure 2).

The book cover had a flatness of less than 5 mm, which is significantly better than the minimum value specified in ISO 18745-1.

Example 2: Passport book cover with coloring and lettering and integrated chip module and antenna

An antenna made of copper wire was placed on a further layer b ') (unprinted) (see also Figure 3). The wire had a diameter of 80 μm and was shaped in the form of an antenna f) in accordance with the ISO 14443 standard for contactless data transmission. At the ends of the antenna, contact was made with a chip module e) which was suitable for data storage and contactless data transmission in accordance with the ISO 14443 standard.

On each of the layers b) and b ') a fin was marked on which the cover of the passport booklet should be folded. The material of layer b) and b ') was removed along the fold line over a width of 6 mm. For this, layers b) and b ') were placed in a press from Plator and a 6 mm wide strip of material was punched out along the fold line by means of a steel strip.

The layers were stacked as shown in Figure 3 and fixed in their position by spot welding at the four corners of the arch.

The film stack according to Figure 3 was laminated on a lamination press from Bürkle. The laminating sheet that was in contact with layer a) was a full-surface Engraved laminate sheet with non-stick coating used. The engraving corresponded to a leather grain. The corresponding sheet was supplied by 4-Plate.

Lamination parameters:

Preheat the press to 150 ° C.

Press for 5 minutes at a pressure of 20 N / cm ² .

After removal of the laminate, the side that was in contact with the engraved metal sheet had a uniform grain of the leather, which could also be perceived as leather. The adhesion of all layers was particularly good, so that a non-destructive separation and reuse of the layers was not possible. The separation of the layers was tested as described in Example 1. The color print remained undamaged after the lamination and appeared with good brilliance through the transparent outer layer a). Furthermore, the passport book cover had a homogeneous thickness distribution throughout. Unevenness due to the laminated antenna and the chip module were taken up by the position dcd ') and compensated, as shown schematically in Figure 4.

The laminates were punched to the size of a passport book cover. The punched-out book cover was then folded along the punched-out recess in the fold line. The folded side of the book cover was then clamped in a roll laminator in a width of 4 mm along the entire catches of the book cover. The book cover was clamped for a period of 3 seconds at a roller temperature of 130 ° C. The book cover was then removed from the rollers. This made it possible to create a memory effect in questions a) and dcd "): If the original shape of the book cover was disturbed by opening, it closed again automatically (Figure 5).

The book cover had a flatness of less than 5 mm, which was significantly better than the minimum value specified in ISO 18745-1.

Example 3: Passport book cover with PEBA and TPU outer layer with coloring and lettering

The layer a), in the form of a layer sequence gh) (consisting of a film g) and a film h), as described for film 2: 2-layer film with the layer sequence (gh)), was arranged so that this was in contact with the printed side of layer b), so that the print was visible through the transparent layer gh).

A line was marked on layer b) where the passport book cover was later folded. The material of layer b) was removed along these fold lines in an area with a width of 6 mm. For this, layer b) was placed in a press from Plator and a 6 mm wide strip of material was punched out along the fold line by means of a steel strip.

Layers g-h) and b) were stacked as shown in Figure 6) and fixed in their position by spot welding at the four corners of the curve.

The stack of layers g-h) and b) was laminated on a Bürkle lamination press. A fully engraved laminating sheet with a non-stick coating was used as the laminating sheet that was in contact with layer g-h). The engraving corresponded to a feather grain. The corresponding sheet was supplied by 4-Plate.

Famination parameters:

Preheat the press to 150 ° C.

Press for 5 minutes at a pressure of 20 N / cm ² .

Cooling under a pressure of 150 N / cm ² until a temperature of 38 ° C. was reached, after which the press was opened.

After removing the laminate, the side that was in contact with the engraved sheet had a uniform feather grain, which could also be perceived as a feather. The color print remained undamaged after the contamination and appeared with good brilliance through the transparent outer layer g-h). The adhesion of all layers was particularly good, so that a non-destructive separation and reuse of the layers was not possible. The separation of the layers was checked by trying to separate the individual layers from one another by hand. The layers could only be separated using appropriate tools (scissors, pliers), which resulted in damage to the layers.

A passport book cover of the desired size was punched out of the laminate. The punched-out book cover was then folded along the punched-out recess in the fold line. The folded side of the book cover was then clamped in a roll laminator in a width of 4 mm along the entire catches of the book cover. The book cover was clamped for a period of 3 seconds at a roller temperature of 130 ° C. The book cover was then removed from the rollers. This enabled a memory effect to be established in the Fage gh): If the original shape of the book cover was changed or disturbed by opening the book cover, it closed again automatically. A slightly opened book cover is shown in Figure 7 with layers gh) and d), as previously described. The book cover had a flatness of less than 5 mm, that is, significantly better than the minimum value of <10 mm specified in ISO 18745-1, whereby measurements were made in accordance with method 9.6 of the standard.

Example 4: Passport book cover made of PEBA and TPU with coloring and lettering and integrated chip module and antenna

In this example 4, a passport book cover with a structure as shown in Figure 3 was produced, with a layer gh) consisting of the foils g) and h), as described above, in contact with the layer b instead of the layer a) ) was brought, the film h) pointing in the direction of layer b).

For this purpose, layer b) was printed in full color on one side. Printing was carried out by means of toner printing on a printer from the manufacturer Ricoh, model MP C3003. In addition to the full-surface color printing, the “Passport” lettering was printed on the already colored layer b).

The layer g-h) was arranged in such a way that it was in contact with the printed side of the layer b) so that the print was visible through the transparent layer a).

An antenna made of copper wire was placed on a further layer IT) (unprinted) (see also Figure 3, with layer a) being replaced by layer g-h)). The wire had a diameter of 80 μm and was shaped in the form of an antenna f) in accordance with the ISO 14443 standard for contactless data transmission. At the ends of the antenna, contact was made with a chip module e) which was suitable for data storage and contactless data transmission in accordance with the ISO 14443 standard.

A line was marked on each of layers b) and IT) where the passport book cover should be folded. The material of layer b) and IT) was removed along the fold line over a width of 6 mm. For this, layers b) and IT) were placed in a press from Plator and a 6 mm wide strip of material was punched out along the fold line using a steel strip.

The layers were stacked as shown in Figure 3 (with layer a) being replaced by layer g-h) and fixed in their position by means of spot welding at the four corners of the curve.

The film stack according to FIG. 3 (with layer a) being replaced by layer gh) was laminated on a lamination press from Bürkle. The laminating sheet that was in contact with the layer gh) was a laminar sheet engraved over the entire area with an anti-stick coating. The engraving corresponded to a leather grain. The corresponding sheet was supplied by 4-Plate. Lamination parameters:

Preheat the press to 150 ° C.

Press for 5 minutes at a pressure of 20 N / cm ² .

After removal of the laminate, the side that was in contact with the engraved metal sheet had a uniform grain of the leather, which could also be perceived as leather. The adhesion of all layers was particularly good, so that a non-destructive separation and reuse of the layers was not possible. The separation of the layers was tested as described in Example 1. The larb print remained undamaged after lamination and appeared with good brilliance through the transparent outer layer g-h). Furthermore, the passport book cover had a homogeneous thickness distribution throughout. Unevenness due to the laminated antenna and the chip module were taken up by the position dcd ') and compensated, as shown schematically in Figure 4. The laminates were punched to the size of a passport book cover. The punched-out book cover was then folded along the punched-out recess in the fold line. The folded side of the book cover was then clamped in a roll laminator to a width of 4 mm along the entire length of the book cover. The book cover was clamped for a period of 3 seconds at a roller temperature of 130 ° C. The book cover was then removed from the rollers. This enabled a memory effect to be achieved in position g-h) and dcd "): If the original Lorm of the book cover was changed by opening, it closed again automatically.

Reference numerals in Figures 1 to 7: a) 150 mhi TPU layer a) b) 250 mhi thick synthetic paper (Teslin ™ from PPG) printed over the entire surface on one side.

b ') 250 μm thick synthetic paper (Teslin ™ from PPG) unprinted dcd') Foil 1 as a TPU three-layer foil with the layer sequence dcd '), the layer c) being present as a foam layer. e) Chip module f) Antenna g) PEBA film h) TPU film

V) Compressed foam

Figure 1 shows the sequence of layers of Example 1 before lamination.

Figure 2 shows the folded laminate from example 1. Figure 3 shows the layer sequence from example 2 before lamination.

Figure 4 shows the layer sequence of Example 2 after lamination.

Figure 5 shows the folded laminate from Example 2

Figure 6 shows the layer sequence of Example 3 before lamination.

Figure 7 shows the folded laminate from Example 3.

Claims

1. A layer structure, preferably a hinge, particularly preferably a book cover, very particularly preferably a book cover for identification or security documents, comprising at least one outer layer a) containing at least one thermoplastic elastomer, in particular a thermoplastic polyurethane, preferably a thermoplastic polyurethane with a hardness from> 60 Shore A according to DIN ISO 7619-1 to <95 Shore D according to DIN ISO 7619-1, particularly preferably with a hardness of> 70 Shore A according to DIN ISO 7619-1 to <95 Shore A according to DIN ISO 7619-1 , and

at least one layer b) containing at least one material selected from the group consisting of a polymer, a metal, a textile, a paper and a synthetic paper or a combination of at least two of these, particularly preferably at least one textile, a paper and / or a synthetic paper.

2. The layer structure according to claim 1, wherein the layer structure, preferably the hinge, particularly preferably the book cover, very particularly preferably the book cover for identification or security documents, has a length x and a width y, the at least one layer b) having at least one Has recess in any shape.

3. The layer structure according to claim 1 or 2, wherein the at least one recess in layer b) has the shape of a parallelogram which runs parallel to a line of symmetry of length x or width y, preferably the parallelogram has a width of> 0, 1 mm to <100 mm, preferably from> 1.0 mm to <50 mm, particularly preferably from> 1.5 mm to <30 mm, very particularly preferably the parallelogram extends over the entire length x or over the entire width y.

4. The layer structure according to claim 1 to 3, wherein the at least one recess of the layer b) over a width of> 0.1 mm to <100 mm, preferably from> 1.0 mm to <50 mm, particularly preferably from> 1 , 5 mm to <30 mm, and particularly preferably over the entire length of the layer structure, or wherein the recess of layer b) is arranged in the form of at least two sections on layer a), so that between the at least two sections at least a recess is formed on the layer a) which is not covered by the layer b), and wherein the at least one recess is preferably over a length of> 0.1 mm to <100 mm, preferably from> 1.0 mm to < 50 mm, particularly preferably from> 1.5 mm to <30 mm, and particularly preferably over the entire width of the layer structure.

5. The layer structure according to claim 1 to 4, wherein the at least one layer b) comprises at least one dye and / or at least one pigment, optionally the layer b) can additionally comprise a printing layer which is applied over the entire and / or part of the area. .

6. The layer structure according to claim 1 to 5, wherein on at least one layer b) a

The printing layer is applied over the whole and / or part of the area, and wherein the printing layer points in the direction of layer a).

7. The layer structure according to claim 1 to 6, wherein the layer a) has a thickness in the range of

> 20 pm to <1000 pm, preferably from> 50 pm to <800 pm, particularly preferably from

> 100 pm to <450 pm.

8. The layer structure according to claim 1 to 7, wherein at least one further layer c) containing at least one thermoplastic polyurethane, which is at least partially designed as a foam layer, and at least one further layer b ') containing at least one material selected from the group consisting of one Polymer, a metal, a textile, a paper and a synthetic paper or a combination of at least two of these, particularly preferably at least one textile, a paper and / or a synthetic paper, is included.

9. The layer structure according to claim 1 to 8, wherein at least one component and / or a functional unit is positioned on the at least one further layer b ′).

10. The layer structure according to claim 8 or 9, wherein the at least one further layer b ') has a recess in any shape, preferably in the form of a parallelogram which runs along a line of symmetry to the length x or width y of the layer structure, which is particularly preferred Recess arranged so that it corresponds in shape and position to the recess in layer b).

The layer structure according to claims 8 to 10, wherein the layer structure comprises at least one further layer d) containing at least one thermoplastic polyurethane with a hardness of> 60 Shore A according to DIN ISO 7619-1 to <95 Shore D according to DIN ISO 7619-1, wherein the layers are arranged so that the sequence a) b) d) c) b ') or a) b) c) d) b') results.

The layer structure according to claim 11, wherein the layer structure comprises at least one further layer d ') comprising at least one thermoplastic polyurethane with a hardness of> 60 Shore A according to DIN ISO 7619-1 to <95 Shore D according to DIN ISO 7619-1, wherein the layers are arranged such that the sequence a) b) d) c) d ") b") or a) b) d ') c) d) b') results.

13. A laminate comprising a layer structure according to claims 1 to 12.

14. The use of the layer structure according to claim 1 to 12 and / or the laminate according to claim 13 for the production of a hinge, preferably a multilayer book cover, particularly preferably a book cover for security and identification documents.

15. A method for producing a multi-layer laminate comprising at least the steps i) providing a layer structure according to claims 1 to 12;

ii) Lamination of the layer structure from step i) at a temperature of> 80 ° C to

<220 ° C and a pressure of> 2 N / cm ² to <500 N / cm ² , preferably lamination with an engraved laminating sheet, particularly preferably with an engraved laminating sheet comprising an anti-stick coating;

iii) optionally folding the layer structure, preferably along the recess in layer b) and optionally in layer b ');

iv) Optional pressing of the layer structure according to step iii) along the recess in layer b) and optionally in layer b '), preferably pressing between two rollers, rolls and / or plates, at a temperature which is> 0.5 ° C to

<150 ° C., preferably> 1 ° C. to <50 ° C., particularly preferably> 1 ° C. to <20 ° C., above the softening temperature of the outer TPU layer a), for a period of 2 to 20 seconds, preferably of 2 to 10 seconds, particularly preferably from 2 to 5 seconds.

v) Optional removal of the layer structure from the press.